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Photodegradation of polymeric and other organic materials

Many polymeric materials are subject to photodegradation. Energetic UV photons have sufficient energy
to disrupt chemical bonds in many materials. Polymers consist of long chains of similar subunits. The
absorption of UV energy can cause the breaking and/or crosslinking of the polymer chains, leading to
altered chemical and mechanical properties. After disruption of the initial chemical state, the polymers
are likely to react with oxygen and/or water vapor causing additional changes. Another type of
photodegradation can occur due to photoabsorption by inorganic pigment particles such as TiO2. An
electron-hole pair is formed in the pigment particle. A photo-excited hole then, for example, can migrate
to the particle’s surface and cause a deleterious chemical reaction in the polymer. For this reason, white
TiO2 pigment particles intended for outdoor use are usually given thin coatings of passivating layers
such as aluminum hydroxide. Many polymer materials are too readily degraded by UV energy to be used
in outdoor applications. Typically, photo-oxidation can be monitored by measuring the infrared
absorption near 6 micrometers caused by oxygen-containing carbonyl (C=O) groups or the absorption
near 3 micrometers due to the hydroxyl (OH) group. One strategy for extending polymer lifetimes is to
add UV absorbers to scavenge the UV photons. Two common inorganic UV absorber pigments are
carbon black and titanium dioxide white. (Both common forms of TiO2, rutile and anatase, switch
abruptly from non-absorptive to absorptive near 400 nm and therefore, while they are white in the
visible spectrum. they are “black” in the UV. Nano-particles of TiO2, with particle size much less than
200 nm, are small enough to be transparent in the visible but are still strong UV absorbers.) Another
option is to choose particularly durable polymers. While TiO2 particles are effective UV absorbers, it
should be mentioned in passing that organic tinted colors (mixtures with TiO2 white) often fade more
readily than “mass tones” (colorant without white). Extensive tables documenting this fading of organic
pigments may be found in the Pigment Handbook [6]. This observation suggests that the short
wavelength part of the visible spectrum (violet, blue) can sometimes be damaging as well. For polymer
coatings on metal roofing, three durable materials are polyester, silconemodified polyester, and PVDF
(polyvinylidene fluoride) [7]. Polyester is inexpensive, and can be used to form hard, scratch-resistant
coatings. However, exposure to UV does cause some chalking. (Chalking is due to surface erosion, which
produces small particles of polymer, and thereby causes a dark surface to look whiter. An empirical scale
of 0 to 10 is sometimes used to characterize chalking [8].). Polyester formulations with longer polymer
chains (higher molecular weight) are more UV resistant than shorter chains. Polyester fabrics are also
used in roofing (and, in sails for sailboats). Single-ply roofing membranes include a polyester fabric for
mechanical strength. Silicone-modified polyesters can provide somewhat improved chalking resistance
and gloss retention relative to unmodified formulations. For factory coating of metal materials (coil
coating), PVDF polymers occupy a premium place in the marketplace. Pure PVDF powder is mixed with
about 30% acrylic copolymer to aid in dispersion during the coating process. Product specifications
[9,10] indicate the weathering performance expected with 10 years 45º south facing Florida exposure:
less than 5 ΔE color change (1 ΔE is the threshold for visual discrimination of differences in lightness or
color), 50% minimum gloss retention, 8 maximum chalk, 10% maximum film erosion. Fence post
exposures in Florida confirm that PVDF-based metal roof coatings are highly durable [11]. The palette of
colors exposed by several manufacturers in south Florida prove that the PVDF-based coatings are very
resistant to climatic soiling because of the marginal loss in solar reflectance (less that 5%) incurred for 15
to 35 year exposures (Figure 1). Since the PVDF-based metal roof coatings are among the most durable
polymeric materials, the above specifications are a good indication of the present day state of the art.
The same specifications [9] indicate that accelerated testing procedures do not correlate well with
actual outdoor exposure tests. In most PVDF coating systems a primer coat of a urethane-based polymer
is used to ensure good adhesion. As urethanes are readily degraded by UV radiation, it is necessary to
ensure that the PVDF topcoat system is a good UV absorber, as can be accomplished with suitable
pigments. This is an example of a general strategy. If outer coatings are sufficiently UV absorbing, more
UV sensitive materials can be used underneath. For example, the use of high chroma colors in
automotive finishes can be enabled with a UV absorbing clear topcoat. Another example is the asphalt
shingle. The color bearing roofing granules must absorb UV efficiently so that UV damage to the asphalt
is minimized. Single-ply roofing membranes are usually based on polymer coatings on a polyester fabric.
Polymers used include EPDM, PVC, and TPO. EPDM is a synthetic rubber termed ethylene propylene
diene monomer. That is, it is three monomers (E, P, and D) polymerized together. PVC is the ubiquitous
polymer polyvinyl chloride. TPO is the industry designation for thermoplastic polyolefin. Polyethylene
and polypropylene are examples of TPOs. Three types of additives are used to enhance the outdoor
stability of single-ply roofing membranes. First, UV absorbing pigments such as carbon black or titanium
dioxide white can be added. Also designated as UVA (UV absorber) are special organic compounds such
as benzophenone and hydroxyphenyl triazine [12]. The use of UV absorbers, of course, does not protect
the surface region of the polymers, because a certain thickness is required to effect absorption.
Important additional types of additive that can help protect the polymer including the surface region are
hindered amine light stabilizers (HALS). HALS molecules do not themselves absorb UV light, but they
react with free radicals (molecular groups with unpaired electrons) formed by UV absorption and
thereby interfere with the photo-oxidation process. One study of accelerated weathering of
polypropylene is prototypical of how many polymeric materials change as they weather [13]. The
surface region of the polymer oxidizes during exposure to UV light in air. Infrared spectroscopy on
microtomed slices of the polymer quantifies the presence of carbonyl (C=O) groups. While the reaction
with oxygen requires the presence of UV light, the extent of oxidation is limited by oxygen diffusion
from the surface into the interior. Figure 2 shows how the oxidation proceeded as a function of
accelerated testing exposure time. Results for samples containing a UV absorbing additive were similar,
but the depth of the penetration of oxygen is diminished. The oxidized surface region is brittle and
cracks readily when the polypropylene film is stretched. After longer exposures, the surface region
cracks spontaneously, indicating that the oxidized region is both brittle and under tensile stress. Wood
shakes and shingles are popular as roofing in some parts of the world. Wood is largely composed of
cellulose, a biopolymer. The cellulose fibers provide strength, and lignin, another biopolymer, acts like
an adhesive to bind the fibers into a matrix. Exposure to UV radiation from the sun changes the wood’s
color, with light colored wood becoming darker, and some darker woods becoming lighter. This color
change is attributed to minor components of wood termed (water soluble) extractives [5]. Lignin also
yellows on UV exposure [14], which indicates that it absorbs short visible wavelengths, i.e., blue.
Exposure to UV also causes damage to the lignin binder, thus leading to detachment of cellulose fibers,
and to erosion of the wood surface. Erosion of a number of bare wood samples mounted vertically with
south facing exposure was in the range of to 0.2 – 1.3 mm over a ten-year period [5]. Thus the erosion
process is slow, although it is somewhat faster for the near-horizontal exposure of wood roofing [15]. An
explicit example of the changing reflectance of wood with environmental exposure is shown in Fig. 3
(from our unpublished measurements). The unweathered sample is a reddish brown, as can be inferred
from the spectrum. The near-infrared reflectance is quite high. After weathering the reflectance drops
(except at short wavelengths), and the resulting color is less reddish, nearly gray. Asphalt is the key
adhesive (binder) material in asphalt shingles. These roofing materials consist of a fiberglass or felt cloth
that is saturated with asphalt and additives, and coated with colored roof granules [16,17]. Asphalt
serves as an adhesive and as a hydrophobic water proofing agent. Asphalt itself is a complex mixture of
hydrocarbons that is a byproduct of the refinement of crude oil into gasoline. In addition to the
predominant hydrogen and carbon atoms, some heteroatoms such as nitrogen, oxygen, and sulfur are
present. The ease of photo-oxidation of asphalt was illustrated in a study of oxygen uptake in 20
micrometer thick asphalt films [18]. Infrared absorption at 1700 cm-1 (5.9 micrometers wavelength) by
the carbonyl group (C=O) increased rapidly in just a few hours of full sun exposure. This study also used
filters to show that short wavelength UV solar photons (320 nm), while few in number, were much more
damaging than longer wavelength UV photons (350 nm). At wavelengths in the visible range (>400 nm),
no photo-oxidation was detected. In addition to increased concentrations of C=O groups, photo-
oxidation also leads to the increased presence of several types of sulfur-oxygen groups including the
sulfate (SO4) group [19]. As a result of oxidation, asphalt becomes harder and embrittled [19.20]. In
order to achieve acceptable weathering lifetimes for asphalt shingles, therefore, it is essential that the
roofing granules absorb the UV component of sunlight. Manufacturers test granules to ensure that they
are efficient UV absorbers. Then, if good coverage of the asphalt substrate is achieved by the roofing
granules, the photo-oxidation process is largely prevented. Organic pigments often have high chroma
(color intensity) and are desirable for product color formulation. Unfortunately rooftop exposure rules
out all but the most durable organics. Application to roof tiles and roof granules, for example, not only
exposes pigments to UV, but also to moisture and reactive pollutants such as SO2 and NOx. Even some
inorganic pigments cannot withstand this weathering. For example ultramarine blue, cadmium sulfide
and cadmium selenide react with oxygen; even carbon black fades to some extent. Durability is
enhanced if the pigment can be isolated from gases in the environment and, particularly, if the pigment
is shielded from the UV. One example of a durable organic pigment in use to color roofing granules is
phthalocyanine (“phthalo”) green. The Pigment Handbook [21] assigns phthalo green an exterior
durability rating of 4-5 on a scale of 1 to 5 (based on 18 months exposure in Florida) and lightfastness
ratings of various formulations in polymer coatings in the range of 6-8 on a scale of 1-8. It is used in
roofing granules together with a durable chromium oxide green to produce a brighter color. After time,
some fading of the phthalo green occurs, and the roof assumes a more muted color. The Pigment
Handbook [6] and the monograph Industrial Organic Pigments [22] are useful references on the
durability of organic pigments. And, of course, the pigment manufacturers are an excellent source of
information of the applicability of pigments for the various specific applications. The preceding few
paragraphs are a very broad overview of the photodegradation of organic materials. This is a mature
and complex subject, covered in monographs [23-26] and journals such as Progress in Organic Coatings,
Polymer Testing, and Polymer Degradation and Stability. An additional interesting reference is the
United Nations’ assessment [27] of effects of increased UV exposure on building materials due to a
decrease in ozone levels in the upper atmosphere.
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UV radiation testing

Ultraviolet radiation (UV) is a specific range of light on the electromagnetic

spectrum. It is invisible to humans because its wavelength range is beyond the
limit of human perception.

UV radiation can impact the performance products and components. Many

natural and synthetic polymers are attacked by ultra-violet radiation, and
products using these materials may crack or disintegrate if they're not UV-stable.
The problem is known as UV degradation, and is a common problem in products
exposed to sunlight. Continuous exposure is a more serious problem than
intermittent exposure, since attack is dependent on the extent and degree of
exposure.

UV degradation in materials testing

UV radiation tests are used to test products and components under solar
radiation conditions. In this process, products and components are subjected to
ultraviolet exposure in a controlled environment. A solar simulator is used to
create ultraviolet radiation and simulate months or years of exposure.

These tests allow us to reproduce the conditions a product is likely to be exposed

to during its life time. Testing is done in accordance with EN 61439-1 Resistance
to ultra-violet (UV) radiation.